CN115483375B - Method for applying silicon-carbon composite material to negative electrode material of lithium ion battery - Google Patents
Method for applying silicon-carbon composite material to negative electrode material of lithium ion battery Download PDFInfo
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 41
- 239000010703 silicon Substances 0.000 claims abstract description 41
- 239000002699 waste material Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000227 grinding Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 20
- 230000002441 reversible effect Effects 0.000 claims abstract description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010405 anode material Substances 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims description 28
- 239000006258 conductive agent Substances 0.000 claims description 23
- 239000002270 dispersing agent Substances 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 238000005520 cutting process Methods 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011889 copper foil Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- 238000002386 leaching Methods 0.000 claims description 9
- 238000011056 performance test Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical group CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 5
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 239000011868 silicon-carbon composite negative electrode material Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 238000000840 electrochemical analysis Methods 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000011870 silicon-carbon composite anode material Substances 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of composite materials and energy storage, and in particular relates to a method for using a silicon-carbon composite material to prepare a lithium ion battery anode material, which comprises the following steps: ball milling waste silicon powder, stirring and mixing the waste silicon powder and an acid solution according to a certain proportion, and calcining the dried and ground waste silicon powder to obtain pretreated silicon powder; mixing acid and hydrogen peroxide in a ratio of 1-3:1, adding silicon powder when heating to 80 ℃, stirring for 3-6 h, centrifuging and washing to obtain a pretreated silicon product; stirring the pretreated silicon product, PY and deionized water in an ice bath, adding ammonium persulfate, stirring for 6-12 h, washing with water after reaching room temperature, centrifuging, drying and grinding, and calcining at 400 ℃ for 1-3 h under an inert atmosphere to obtain the silicon product. The invention has the advantages of no doping, simple reaction condition, low price of the used solvent, no toxicity and no harm, and the synthesized negative electrode material has higher reversible specific capacity, multiplying power performance, cycle performance and long cycle life, and is favorable for meeting the actual demands.
Description
Technical Field
The invention belongs to the technical field of composite materials, relates to a composite electrode material, and in particular relates to a preparation method of a silicon-carbon composite material and application of the silicon-carbon composite material in lithium storage.
Background
The energy crisis is one of the most urgent problems in the twenty-first century, the urgent need for energy is continuously increased along with the rapid development of economy, people begin to pay attention to the development and utilization of new energy, the quick development of the solar energy industry is involved, a great amount of waste silicon left by cutting of solar crystalline silicon is generated, a great amount of resource waste is caused, the existing means for treating the waste silicon are complex in operation and low in utilization rate, and therefore, how to effectively recycle and utilize the waste silicon to achieve the maximum resource utilization has important significance.
Silicon element was applied to the negative electrode of ion battery since 1970, and the theoretical specific capacity of silicon is even up to 4200mA h g -1 Is more than 10 times that of a carbon-based material, and is considered as the most competitive anode material of the next generation based on the high specific capacity of a silicon material. However, silicon base is not completely used as a cathode material, and the volume expansion of the cathode material can reach 300% in the charge and discharge process, so that the crushing of silicon particles and the cracking of SEI films are caused, the cycle performance of a battery is greatly influenced, and the service performance of the battery is influenced. There is a method that not only can the stress generated by the volume expansion of silicon be relieved by carbon coating, but also the conductivity of the silicon anode material can be increased. In addition, the first step in commercialization is to reduce the cost, thereby realizing the production of commercial applications. Therefore, it is important to find simple and inexpensive, pollution-free silicon raw materials and to develop simple and efficient preparation processes.
Disclosure of Invention
The invention solves the technical problems that: the resource utilization of waste silicon and the problem of poor cycling stability caused by the volume expansion of a lithium ion battery are solved as electrode materials. The solar crystalline silicon cutting waste and PY carbon source adopted by the invention are compounded, so that the preparation process is simple, the operation is convenient, the price is low, the environment is protected, the problem of recycling the solar crystalline silicon waste is effectively solved, the recycling of the crystalline silicon waste is realized, and the specific discharge capacity of the crystalline silicon waste in the first cycle can reach 2400mAh g -1 It is at 0.1, 0.25, 0.5, 1A g -1 The initial reversible capacity under current density is respectively as high as 1431, 941, 747 and 590mAh g -1 After 100 cycles, the reversible capacity of the material can still reach 451mAh g -1 Has excellent multiplying power and cycle performance.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a method for using silicon-carbon composite material as negative electrode material of lithium ion battery includes the following steps:
A. ball milling is carried out on silicon source precursor crystal silicon cutting waste silicon, the ball/solid mass ratio is 10-20:1, the waste silicon after ball milling is pickled, the leaching temperature is 15-25 ℃, the leaching time is 3-12 h, the volume of leaching liquid and the mass ratio of cutting waste are 20-200 mL:1g, and the stirring speed is 100-500 r/min; drying and grinding waste silicon washed by acid washing water, and calcining the obtained powder for 1-5 hours at 600-900 ℃ in inert atmosphere to obtain pretreated silicon powder;
B. mixing acid and hydrogen peroxide according to a volume ratio of 1-3:1, cooling to room temperature, heating to 80 ℃ in an oil bath, adding the silicon powder obtained in the step A into the solution, and stirring for 3-6 hours to obtain a suspension; washing the suspension with water, centrifuging, and drying to obtain a product with hydroxyl silicon attached to the surface;
C. and B, respectively carrying out 100mg of hydroxyl silicon product, pyrrole PY and deionized water on the surface of the product obtained in the step B: 400ul:50ml, adding ice cubes into a beaker, stirring uniformly, and adding ammonium persulfate and PY according to the following formula 1:2, continuing ice bath stirring for 12 hours, after finishing the temperature recovery to room temperature, washing with water, centrifuging, drying, heating the tube furnace from room temperature to 400 ℃ in an inert atmosphere, and preserving the heat for 1 hour to obtain the silicon-carbon composite material;
D. c, mixing and grinding the silicon-carbon composite material prepared in the step C, a conductive agent and a binder according to a ratio of 8:1:1, adding a proper amount of dispersing agent for dissolution grinding, coating the mixture on a copper foil after grinding until no particles exist, drying for 8-12 h, and cutting 1 x 1cm 2 The size of the lithium ion semi-battery is used as a negative plate, and the lithium ion semi-battery is obtained by assembling the positive plate, the negative plate, the diaphragm, the gasket and the electrolyte in a glove box.
Preferably, the silicon source precursor in the step A is silicon as a silicon cutting waste.
Preferably, in step C pyrrole is a carbon source precursor.
Preferably, the acid mass fraction in the step B is 5-15% of nitric acid or sulfuric acid.
Preferably, the inert gas in the step C is argon or nitrogen.
Preferably, the carbonization in the steps A and C is carried out by using a tube furnace or a box furnace with the heating rate of 3-15 ℃/min -1 。
Preferably, the negative electrode sheet is formed by coating a negative electrode active material, a conductive agent, a dispersing agent and a binder on the surface of a copper foil, wherein the negative electrode active material is a silicon-carbon composite material; the conductive agent is Ketjenback EC-600JD which is Ketjenback conductive carbon black; the dispersing agent is Nitrogen Methyl Pyrrolidone (NMP); the binder is an oily binder polyvinylidene fluoride (PVDF); the electrolyte is 1M lithium hexafluorophosphate (LiPF) 6 )。
Preferably, the coated anode material is assembled into a 2032 button battery by taking a lithium sheet as a counter electrode and Celgerd2400 as a diaphragm in a glove box, cyclic voltammograms are measured at different scanning rates under a potential window of 0.01-1.5V, and the rate performance and the long-cycle performance are tested at different current densities.
Advantageous effects
The solar crystalline silicon cutting waste and PY carbon source adopted by the invention are compounded, so that the preparation process is simple, the operation is convenient, the price is low, the environment is protected, the problem of recycling the solar crystalline silicon waste is effectively solved, the silicon-based anode material wrapped by carbon has good conductivity, the recycling of the crystalline silicon waste is realized, and meanwhile, the electrode material also has good multiplying power performance and long cycle stability.
The invention coats a layer of compact PPy carbon material on the surface of the waste silicon, has simple reaction operation and low precursor cost, can realize the recycling of resources, and has great application potential due to the composite environment-friendly concept. The synthesized composite material can provide more reaction sites for lithium ions, has larger specific surface area, can also help the electrode material to provide more contact area with electrolyte, realizes the improvement of the capability of storing lithium ions, and is assembled with a lithium sheet to form a half cell for performance test.
In example 1, PY and ammonium persulfate are reacted according to 400 mu L and 200mg respectively, and when a charge and discharge test is carried out on a half cell assembled by the obtained anode material, the specific discharge capacity of the half cell in the first circle can reach 2400mAh g -1 At the same time, has the best multiplying power performance, namely when the current density is 0.1A g -1 、0.25Ag -1 、0.5A g -1 、1A g -1 The initial reversible capacity can reach 1431, 941, 747 and 590mAh g respectively -1 After 100 cycles, the reversible capacity of the material can still be stabilized at 451mAh g -1 。
In example 2, PY and ammonium persulfate are reacted according to 200 mu L and 100mg respectively, and when a charge-discharge test is carried out on a half cell assembled by the obtained anode material, the specific discharge capacity of the half cell in the first circle can reach 2083mAh g -1 At the same time, has the best multiplying power performance, namely when the current density is 0.1, 0.25, 0.5 and 1Ag -1 The initial reversible capacity can reach 1259, 832, 641, 504mAh g respectively -1 After 100 cycles, the reversible capacity of the material is stabilized at 406mAh g -1 。
In example 3, PY and ammonium persulfate were reacted at 800. Mu.L and 400mg, respectively, and the resulting half cell assembled from the negative electrode material had a specific discharge capacity of 1950mAh g in the first cycle when tested for charge and discharge -1 At the same time, has the best multiplying power performance, namely when the current density is 0.1, 0.25, 0.5 and 1A g -1 The initial reversible capacity can reach 1083, 695, 556 and 450mAh g respectively -1 After 100 cycles, the reversible capacity of the material is stabilized at 396mAh g -1 。
The multiplying power performance, the higher reversible specific capacity and the long cycle life which are shown after the half batteries assembled by the three silicon-carbon composite materials are tested are all more excellent than those of the original silicon-based negative electrode material, so that the actual requirements are favorably met. The rate performance in example 1 was the best for long cycle stability.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the silicon-carbon composite anode material prepared in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the silicon-carbon composite anode material prepared in example 2;
FIG. 3 is an X-ray powder diffraction pattern (XRD) of the silicon-carbon composite anode material prepared in example 1;
FIG. 4 shows a Raman spectrum (Raman) of the silicon-carbon composite anode material prepared in example 1;
FIG. 5N of the silicon carbon composite negative electrode material prepared in example 1 2 An adsorption and desorption curve;
FIG. 6. Rate and cycle performance curves of the silicon carbon composite negative electrode material prepared in example 1 after use in a lithium ion battery;
FIG. 7 shows the rate and cycle performance curves of the silicon-carbon composite anode material prepared in example 2 after it is used in a lithium ion battery;
FIG. 8 shows the rate and cycle performance curves of the silicon-carbon composite anode material prepared in example 3 after it is used in a lithium ion battery;
FIG. 9 shows the rate and cycle performance curves of the silicon-carbon composite anode material prepared in example 4 after it is used in a lithium ion battery;
Detailed Description
The present invention will be described in detail with reference to the following examples, so that those skilled in the art can better understand the present invention, but the present invention is not limited to the following examples.
Example 1
A method for preparing a silicon-carbon composite material, comprising: ball milling is carried out on solar crystalline silicon waste, the ball/material mass ratio is 20:1, and the ball milled waste silicon is subjected to HCL and HNO 3 Acid washing is carried out under the condition that the volume ratio is 2:1, the leaching temperature is room temperature under the acid washing condition, the leaching time is 12h, and the volumes of the cutting waste and the leaching liquid are 1g: mixing the solid and the liquid at a solid-liquid ratio of 4ml, wherein the stirring speed is 300r/min, and the stirring time is 30h; drying and grinding waste silicon washed by acid washing water, and adding the waste silicon into N 2 Calcining for 1h at 700 ℃ in atmosphere to obtain pretreated silicon powder; mixing sulfuric acid and hydrogen peroxide according to a volume ratio of 3:1, cooling to room temperature, heating to 80 ℃ in an oil bath, adding pretreated silicon powder into the solution, and stirring for 6 hours to obtain a suspension; washing, centrifuging and drying to obtain a surface with a hydroxyl silicon product, so as to realize pretreatment;
respectively taking 100mg of the pretreated PY with the surface attached with the hydroxyl silicon product and 400ul of PY into 50ml of deionized water, freezing in a refrigerator for 1h, uniformly stirring in an ice bath, adding 200mg of ammonium persulfate, adding ice blocks into a beaker for ice bath, stirring for 12h, washing and centrifuging when the solution returns to room temperature,drying, collecting solid, grinding, and then N 2 Calcining the sample in a tube furnace under the atmosphere, heating to 400 ℃ from room temperature, and preserving heat for 1h to obtain the PPY carbon source/waste silicon composite material.
Mixing and grinding the prepared silicon-carbon composite material, a conductive agent and a binder according to a ratio of 8:1:1, adding a proper amount of dispersing agent for dissolution grinding, coating the mixture on a copper foil after grinding until no particles exist, drying for 8-12 h, and cutting 1 x 1cm 2 The size of the lithium ion half battery is used as a negative electrode plate, and the lithium ion half battery is obtained by assembling the positive electrode plate, the negative electrode plate, the diaphragm, the gasket and the electrolyte in a glove box.
The negative electrode sheet is formed by coating a negative electrode active material, a conductive agent, a dispersing agent and a binder on the surface of a copper foil, wherein the negative electrode active material is a silicon-carbon composite material; the conductive agent is Ketjenback EC-600JD which is Ketjenback conductive carbon black; the dispersing agent is Nitrogen Methyl Pyrrolidone (NMP); the binder is an oily binder polyvinylidene fluoride (PVDF).
Commercial lithium sheet is a counter electrode, and electrolyte is LiPF 6 And (3) using the electrolyte, celgard 2500 as a diaphragm, using the prepared silicon-carbon composite anode material as a working electrode, assembling the working electrode together to form a button cell, and carrying out electrochemical performance test on the button cell.
As can be seen from fig. 1, the particle size of the prepared silicon-carbon composite electrode material is in the micrometer scale.
As can be seen from FIG. 3, the positions and the relative intensities of the diffraction peaks of the prepared silicon-carbon composite electrode material are consistent with those of the JPCDS card (# 27-1402), which shows that the product is the silicon-carbon composite material.
The raman spectra of fig. 4 show peaks of silicon and carbon, which also represent the degree of disorder of carbon, indicating that the product is a silicon-carbon composite.
N in FIG. 5 2 The absorption and desorption curve shows that the specific surface of the composite material reaches 737.3813m 2 And/g, mainly in the form of micropores and mesopores.
The electrochemical test results in fig. 6 show that the silicon-carbon composite material prepared in this example, the conductive agent and the binder are manufactured into an electrode according to the ratio of 8:1:1, and the electrode and the lithium sheet are assembled into a half cell for performance testThe specific discharge capacity of the material in the first cycle can reach 2400mAh g -1 It is at 0.1, 0.25, 0.5, 1A g -1 The initial reversible capacity under current density is respectively as high as 1431, 941, 747 and 590mAh g -1 After 100 cycles, the reversible capacity of the material can still reach 451mAh g -1 Has excellent multiplying power and cycle performance.
Example 2
A method for preparing a silicon-carbon composite material, comprising: respectively taking 100mg of pretreated silicon product and 200ul of PY into 50ml of deionized water, freezing in a refrigerator for 1h, stirring uniformly in an ice bath, adding 100mg of ammonium persulfate, stirring in an ice bath for 12h, recovering the solution to room temperature, washing, centrifuging, drying, collecting solid, grinding, and N 2 Calcining the sample in a tube furnace under the atmosphere, heating to 400 ℃ from room temperature, and preserving heat for 1h to obtain the PPY carbon source/waste silicon composite material.
Mixing and grinding the silicon-carbon composite material prepared in the example, a conductive agent and a binder according to a ratio of 8:1:1, adding a proper amount of dispersing agent for dissolution and grinding, coating the mixture on a copper foil after the mixture is ground to be free of particles, drying the mixture for 8-12 hours, and assembling the mixture in a glove box by using a positive plate, a negative plate, a diaphragm, a gasket and an electrolyte to obtain the lithium ion half battery.
The negative electrode sheet is formed by coating a negative electrode active material, a conductive agent, a dispersing agent and a binder on the surface of a copper foil, wherein the negative electrode active material is a silicon-carbon composite material; the conductive agent is Ketjenback EC-600JD which is Ketjenback conductive carbon black; the dispersing agent is Nitrogen Methyl Pyrrolidone (NMP); the binder is an oily binder polyvinylidene fluoride (PVDF).
Commercial lithium sheet is a counter electrode, and electrolyte is LiPF 6 And (3) using the electrolyte, celgard 2500 as a diaphragm, using the prepared silicon-carbon composite anode material as a working electrode, assembling the working electrode together to form a button cell, and carrying out electrochemical performance test on the button cell.
Fig. 2 shows that the particle size of the prepared silicon-carbon composite electrode material is in the micrometer scale.
As can be seen from FIG. 3, the positions and the relative intensities of the diffraction peaks of the prepared silicon-carbon composite electrode material are consistent with those of the JPCDS card (# 27-1402), which shows that the product is the silicon-carbon composite material.
The test results in fig. 7 show that the silicon-carbon composite material prepared in the embodiment, the conductive agent and the binder are manufactured into an electrode according to the ratio of 8:1:1, and are assembled into a half cell with a lithium sheet, and the performance test is performed, wherein the initial specific discharge capacity can reach 2083mAh g -1 It is at 0.1, 0.25, 0.5, 1A g -1 Initial reversible capacities at current densities of up to 1259, 832, 641, 504mAh g, respectively -1 After 100 cycles, the reversible capacity of the material can still reach 406mAh g -1 。
Example 3
A method for preparing a silicon-carbon composite material, comprising: respectively taking 100mg of pretreated silicon product and 800ul of PY into 50ml of deionized water, freezing in a refrigerator for 1h, stirring uniformly in an ice bath, adding 400mg of ammonium persulfate, stirring in an ice bath for 12h, recovering the solution to room temperature, washing, centrifuging, drying, collecting solid, grinding, and adding N 2 Calcining the sample in a tube furnace under the atmosphere, heating to 400 ℃ from room temperature, and preserving heat for 1h to obtain the PPY carbon source/waste silicon composite material.
Mixing and grinding the silicon-carbon composite material prepared in the example, a conductive agent and a binder according to a ratio of 8:1:1, adding a proper amount of dispersing agent for dissolution and grinding, coating the mixture on a copper foil after the mixture is ground to be free of particles, drying the mixture for 8-12 hours, and assembling the mixture in a glove box by using a positive plate, a negative plate, a diaphragm, a gasket and an electrolyte to obtain the lithium ion half battery.
The negative electrode sheet is formed by coating a negative electrode active material, a conductive agent, a dispersing agent and a binder on the surface of a copper foil, wherein the negative electrode active material is a silicon-carbon composite material; the conductive agent is Ketjenback EC-600JD which is Ketjenback conductive carbon black; the dispersing agent is Nitrogen Methyl Pyrrolidone (NMP); the binder is an oily binder polyvinylidene fluoride (PVDF).
Commercial lithium sheet is a counter electrode, and electrolyte is LiPF 6 Electrolyte, celgard 2500 as a diaphragm, prepared silicon-carbon composite anode material as a working electrode, and assembled into a button cell together, and subjected to electrochemical performance test。
As can be seen from FIG. 3, the positions and the relative intensities of the diffraction peaks of the prepared silicon-carbon composite electrode material are consistent with those of the JPCDS card (# 27-1402), which shows that the product is the silicon-carbon composite material.
The test results in fig. 8 show that the silicon-carbon composite material prepared in the embodiment, the conductive agent and the binder are manufactured into an electrode according to the ratio of 8:1:1, and are assembled into a half cell with a lithium sheet, and the performance test is performed, wherein the initial specific discharge capacity is 1950mAh g -1 At 0.1, 0.25, 0.5, 1A g -1 The initial reversible capacity under the current density is up to 1083, 695, 556 and 450mAh g respectively -1 After 100 cycles, the reversible capacity of the material can still reach 396mAh g -1 。
Example 4
Taking silicon materials (the granularity range is 1-100 mu m) of solar crystalline silicon cutting waste, using ethanol as a dispersing agent and a solvent to dissolve organic matters remained in a sample, adopting a ball mill to grind the waste silicon aggregate into powder, setting the rotation speed of the ball mill to 300r/min, and ball-milling the powder for 30h; washing waste silicon after ball milling with acid washing water, and removing metal elements and some impurities remained in the waste silicon in the cutting process by acid washing under the conditions of HCl (volume fraction is 36.0% -38.0%) and HNO 3 (volume fraction is 65.0% -68.0%), volume ratio is 2:1, and the cleaned waste silicon is centrifugally dried and ground to obtain a powdery sample in N 2 And (3) performing heat treatment under the atmosphere, wherein the temperature is raised to 700 ℃, the heat preservation is performed for 1h, and the heating rate is 10 ℃/min. Calcining the sample by a tube furnace to obtain pretreated silicon powder.
Mixing and grinding the silicon-carbon composite material prepared in the example, a conductive agent and a binder according to a ratio of 8:1:1, adding a proper amount of dispersing agent for dissolution and grinding, coating the mixture on a copper foil after the mixture is ground to be free of particles, drying the mixture for 8-12 hours, and assembling the mixture in a glove box by using a positive plate, a negative plate, a diaphragm, a gasket and an electrolyte to obtain the lithium ion half battery.
The negative electrode sheet is formed by coating a negative electrode active material, a conductive agent, a dispersing agent and a binder on the surface of a copper foil, wherein the negative electrode active material is a silicon-carbon composite material; the conductive agent is Ketjenback EC-600JD which is Ketjenback conductive carbon black; the dispersing agent is Nitrogen Methyl Pyrrolidone (NMP); the binder is an oily binder polyvinylidene fluoride (PVDF).
Commercial lithium sheet is used as a counter electrode, and electrolyte is LiPF 6 And the electrolyte, celgard 2500, is taken as a diaphragm, pretreated silicon powder is taken as a working electrode, and the pretreated silicon powder is assembled into a button cell together, and electrochemical performance test is carried out on the button cell for comparison.
The test results in fig. 9 show that the silicon powder treated in this example was fabricated into electrodes with conductive agent and binder at a ratio of 8:1:1, and assembled into half cells with lithium sheets for performance testing at 0.1, 0.25, 0.5, 1Ag -1 Charging and discharging are carried out under the current density, and the initial discharge specific capacity can reach 1454, 19, 7 and 4mAh g -1 After 100 cycles, the reversible capacity of the material can be maintained at 19mAh g -1 The untreated silicon powder has the advantages of quick capacity decay and poor circulation stability.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.
Claims (1)
1. A method for using a silicon-carbon composite material to prepare a lithium ion battery anode material is characterized by comprising the following steps: the method comprises the following steps:
ball milling is carried out on solar crystalline silicon waste, the ball/material mass ratio is 20:1, and the ball milled waste silicon is subjected to HCL and HNO 3 Acid washing is carried out under the condition that the volume ratio is 2:1, the leaching temperature is room temperature under the acid washing condition, the leaching time is 12h, and the volumes of the cutting waste and the leaching liquid are 1g: mixing the solid and liquid ratios of 4 and ml, wherein the stirring speed is 300r/min, and the stirring time is 30h; drying and grinding waste silicon washed by acid washing water, and adding the waste silicon into N 2 Calcining for 1h at 700 ℃ in atmosphere to obtain pretreated silicon powder; mixing sulfuric acid and hydrogen peroxide according to a volume ratio of 3:1, cooling to room temperature, heating to 80 ℃ in an oil bath pot, and adding pretreated silicon powder into the solutionStirring the mixture in the solution for 6 hours to obtain suspension; washing, centrifuging and drying to obtain a surface with a hydroxyl silicon product, so as to realize pretreatment;
respectively taking 100mg of the pretreated silicon product with hydroxyl groups and 400ul of pyridine on the surface, placing in 50ml of deionized water, freezing in a refrigerator for 1h, stirring uniformly in an ice bath, adding 200mg of ammonium persulfate, adding ice blocks into a beaker for ice bath, stirring for 12h, recovering the solution to room temperature, washing with water, centrifuging, drying, collecting solids, grinding, and adding N 2 Calcining the sample in a tube furnace under the atmosphere, heating to 400 ℃ from room temperature, and preserving heat for 1h to obtain a carbon-silicon composite material;
mixing and grinding the prepared silicon-carbon composite material, a conductive agent and a binder according to a ratio of 8:1:1, adding a proper amount of dispersing agent for dissolution grinding, coating the mixture on a copper foil after grinding until no particles exist, drying for 8-12 hours, and cutting to 1X 1cm 2 The size of the lithium ion half battery is used as a negative electrode plate, and the lithium ion half battery is obtained by assembling the positive electrode plate, the negative electrode plate, the diaphragm, the gasket and the electrolyte in a glove box;
the negative electrode sheet is formed by coating a negative electrode active material, a conductive agent, a dispersing agent and a binder on the surface of a copper foil, wherein the negative electrode active material is a silicon-carbon composite material; the conductive agent is Ketjenback EC-600JD which is Ketjenback conductive carbon black; the dispersing agent is nitrogen methyl pyrrolidone; the binder is oily binder polyvinylidene fluoride;
commercial lithium sheet is a counter electrode, and electrolyte is LiPF 6 Electrolyte, celgard 2500 is a diaphragm, the prepared silicon-carbon composite negative electrode material is a working electrode, and the working electrode and the silicon-carbon composite negative electrode material are assembled into a button cell together, and electrochemical performance test is carried out on the button cell;
electrochemical test results show that the prepared silicon-carbon composite material, the conductive agent and the adhesive are manufactured into an electrode according to the ratio of 8:1:1, and the electrode and the lithium sheet are assembled into a half battery, and the performance test is carried out, wherein the specific capacity of the half battery in the first cycle of discharge can reach 2400mAh g -1 At 0.1, 0.25, 0.5, 1A g -1 The initial reversible capacity at current density was 1431, 941, 747, 590mAh g -1 After 100 cycles, the reversible capacity of the material is 451mAh g -1 。
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